Viability of Dyeing of Natural and Viability of Dyeing of Natural and Synthetic FibersSynthetic Fibers with Nanopigments in with Nanopigments in

Supercritical COSupercritical CO22

Bàrbara Micó, Verónica Marchante,Francisco Martínez-Verdú, Eduardo Gilabert

Ciencia y Tecnología del ColorSeminario 2009

ÍNDEX Introduction

Supercritical CO2

Dyeing in supercritical CO2

Nanopigments and nanoclays Objectives State of the art

Colorant selection Fibres Process variables

Challenges Solutions / Future perspectives Advantages of using Nanopigments References / Acknowledgements

INTRODUCTION Supercritical CO2 : Solvent Properties

Low cost Non-Toxic Density: liquid Viscosity: Gas Recycling up to 90% Inert Non-explosive Low critical point

Pressure: 73.858 ± 0.005 bar Temperature: 31.05 ± 0.05 ºC

ADVANTAGESNo waste water

(problem in textile industry)

No require additivesNo final dryingRecycling

Solvent Colorants

Environmental friendly

DYEING IN SUPERCRITICAL CARBON DIOXIDE DRAWBACKS

Investment Solve colorantsTime of process

NANOPIGMETS NANONATERIALS: since 90’s

Hybrid materials consisting of organic dyes and layered silicate nanoparticles

Nanoclay: particle size < 20nm Ionic-exchange reaction: Colorant + Nanoclay

(H+)Nanoclays: Smectite group

Montmollonite: laminar Sepiolite: acicular

Scheme of nanopigments’ synthesis at laboratory Nanoclay

SievingH2O deionized

Dispersion

Stag

e 1

+

Colorant solution

Ionic Exchange

Washing and Filtering

Drying

Stag

e 2

APLICATIONS:- Coloration of Plastics- Printing Inks- Functional materials

Schematic representation of clay sheet, dye molecule (methylene blue) and blue Nanopigment.

Capa de arcilla

Azul de metileno

Capa de arcilla

OBJECTIVES: PROJECT AITEX-AINIA-UA1.

STA

TE O

F TH

E A

RT

2. SELECTION/MATERIAL DEVELOPMENT

3. DISSOLUTION OF MATERIALS IN SC CO2

4. POLYMER IMPREGNATION IN SC-CO2

6. REENGINIEERING

5. CHARACTERIZETREATED MATERIAL

WITH SC-CO2

7. VIABILITY / ECONOMIC

8. R

ESU

LTS

AN

D D

OFU

SIO

N

2.1. POLIMERS 2.2. COLORANTS 2.3.AGENTS ANTIBACTERIAL

Colorants that can be solved in scCO2

Textile dyes classification:DirectsReactiveAcids/BasicsSulphurVatMordantDispersePigments

STATE OF THE ART

NOT DISSOLVED IN SC- CO2

DISSOLVED IN SC-CO2

Azoic [ N N ]The most important disperse dyesCheaper and easy manufacture From non polar fibers

DISPERSE DYESCOLORANT SELECTION

Anthraquinone It’s more soluble [1]More expensive

MORE SOLUBILITY

REACTIVE DISPERSE DYES [2]

(mono-di-)chlorotriazine Dyeing of natural fibers Protein or synthetic fibers

COLORANT: SELECTION

(mono-di-)-fluorotriazine Dyeing cotton Using different co-solvents Methanol improves the

solubility REACTIVE GROUPS CHANGE THE COLORANT’S SOLUBILITY

N N

N ClR

Colorante

+ Fibra-OH N N

NR

Colorante

O Fibra

Fibre

Colorant

Fibre

Colorant

Vinylsulphone : Improve fixations [3] Are suitable for dyeing textiles containing polyester,

nylon, silk or wool. Fixations between 70 – 90%

REACTIVE DYESCOLORANT SELECTION

Solubility : [4]

-Decrease: OH, NH2,COOR’-Increase: HX NO2

[X=F,Cl,Br,..]

Dyeing stepsTransport of dye to the fibres: SOLUBILITY

Works: different cosolventsAcetonitrileMethanolWaterAcetone

Reaction of the dye with the textile: AFFINITYDIFFUSSION of dye into the fibres: D coefficient.

PROCESS VARIABLES

IMPROVE THE RESULTS REACTIVE

GROUPS

PARTICLE SIZE

EQUIPMENTS

Gas cylinder

Carbon dioxide pump

Pump head cooler

Cosolvent reservoir

Cosolvent pump

Stop valves

Pressure gauge Back pressure

regulator

Dyeing vessel

StirrerHeating jacket

Dyeing beam

Planta FSC500

EQUIPMENTS: AINIA PILOT PLANT

Planta PFS20

Planta SFF-58_60

PET the most studied Changes in the structure of polymers:

Plastics: >TgSize stability

Natural fibres [5]

Pre-treatments: Hydrophobic and nonpolar Polyurethane DMDHEU Solvents: Alcohol and water

FIBRES

CHALLENGES We only can use non polar colorants in scCO2: These kind of colorant haven’t affinity of natural

fibres. There are a lot of variables in the process: Solubility

can change with: Colorants (Reactive group, Particle size…) Pressure Temperature Substrates: Natural or synthetic fibers

The time of process is too long: 4h

SOLUTIONS / FUTURE PERSPECTIVES Pre-treated fibres:

PET: with UV, N,N-dimethylacrylamideCO: DMDHEU, PUR, acetone…

Changes in structure of colorants [6] Novel reactive disperse dyes has been synthesized.

Control the solubility and dye process.Equations to predict the solubility.

NANOPIGMENTS

ADVANTAGES OF NANOPIGMENTS Nanopigments are a viable and environmental-

friendly alternative to traditional pigments because of their easy synthesis and conventional processing.

Increase the color gamut: We can use a lot of conventional organic dyes.

Increase the resistance of colors: UV, O2, Temperature

Improve substrate properties: stability, strength, permeability…

REFERENCESREFERENCES[1] S. N. Joung et all. “Solubility of Disperse Anthraquinone and Azo Dyes in Supercritical Carbon Dioxide at 313.15 to 393.15 K and from 10 to 25 MPa” J. Chem. Eng. 43, 9-12. 1998[2] M.V. Fernandez et all “A significant approach to dye cotton in supercritical carbon dioxide with fluorotriazine reactive dyes” J. of Supercritical Fluids 40 477–484. 2007[3] M. van der Kraan et all. “Dyeing of natural and synthetic textiles in supercritical carbon dioxide with disperse reactive dyes” J. of Supercritical Fluids 40 470–476. 2007[4] Gerardo A. Montero et all. “Supercritical Fluid Technology in Textile Processing: An Overview” Ind. Eng. Chem. Res., 39, 4806-4812. 2000[5] P. L. Beltrame, et all.“Dyeing of Cotton in Supercritical Carbon Dioxide”. Dyes and Pigments, 39, 335-340. 1998 [6] Andreas Schmidt, Elke Bach and Eckhard Schollmeyer. “Supercritical fluid dyeing of cotton modified with 2,4,6-trichloro-1,3,5-triazine”. Color. Technol., 119. 2003

This work is supported by Ministry of Science and Innovation (MICINN) with the project “Aplicación de la tecnología de fluidos supercríticos en la impregnación de sustratos poliméricos” ref.: CIT-20000-2009-2.

AcknowledgementsAcknowledgements